N-acyl-amino acid derivatives for improvement of the flavour profile of edible compositions

Abstract

The use of a compound according to formula (I) or the edible salts thereof in an edible composition to mask or modulate an undesired taste or off-taste contained in the edible composition ##STR00001##
wherein
R.sub.1 is an alkyl residue containing 6 to 20 carbon atoms, or an alkene residue containing from 9 to 25 carbon atoms with 1 to 6 double bonds, R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid, in particular a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

Claims

1. A method of masking or modulating an undesired taste or off-taste contained in an edible composition, the method comprising the step of: including in the edible composition 1 ppb -10 ppm of a compound selected from the group consisting of: N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro, N-linolenoyl-Pro; N-geranoyl-Met, N-palmitoyl-Met, N-palmitenoyl-Met, N-stearoyl-Met, N-oleoyl-Met, N-linoleoyl-Met, N-linolenoyl-Met, and edible salts thereof selected from chlorides, sulphates, phosphates, gluconates, sodium, citrates, carbonates, acetates and lactates.

2. An edible composition comprising an ingredient which imparts an undesired taste or off-taste, and a compound present in the edigle composition in a concentration of 1 ppb-10 ppb selected from the group consisting of: N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro, N-linolenoyl-Pro; N-geranoyl-Met, N-palmitoyl-Met, N-palmitenoyl-Met, N-stearoyl-Met, N-oleoyl-Met, N-linoleoyl-Met, N-linolenoyl-Met, and edible salts thereof selected from chlorides, sulphates, phosphates, gluconates, sodium, citrates, carbonates, acetates and lactates.

3. An edible composition according to claim 2 wherein the ingredient which imparts an undesired or off-taste is selected from the group consisting of: flavanoids, polyphenols, peptides, minerals, terpenes, caffeine, taurine, carnitine, glucorolactone, guarana, vitamins, minerals, amino acids, proteins or protein analogs, peptides, antioxidants, KCl, soy, a soy-based ingredient, sugar substitutes selected from natural sweeteners, and synthetic high intensity sweeteners, dairy substitutes, pharmacological actives, enzyme modified cheese, oral care actives selected from, chlorohexidine (gluconate), cetyl pyridinium chloride, tego-betaine and metal salts selected from stannous salts and zinc salts, whey, casein, tannins, products selected from coffee products, tea products, mouthwash and toothpaste, and preservatives selected from sodium benzoate and potassium sorbate.

4. An edible composition according to claim 3 wherein said ingredient is a natural sweetener selected from: sucrose, high fructose corn syrup, fructose and glucose, or is a high intensity, non-nutritive sweetener selected from: aspartame, acesulfame K, sucralose, cyclamate, sodium saccharin, neotame, and rebaudioside A.

5. An edible composition according to claim 3 wherein the ingredient is soy or a soy-based ingredient.

6. An edible composition according to claim 2 in the form of a powdered soft drink or a dry mix composition.

7. An edible composition according to claim 2 in the form of a snack food.

8. An edible composition according to claim 2 in the form of an alcoholic beverage.

9. An edible composition according to claim 2 in the form of an orally administrable tablet, capsule, powder or multiparticulate.

10. An edible composition according to claim 2 in the form of a caloric or non-caloric beverage containing a natural sweetener selected from: sucrose, high fructose corn syrup, fructose and glucose, or a high intensity, non-nutritive sweetener selected from: aspartame, acesulfame K, sucralose, cyclamate, sodium saccharin, neotame, rebaudioside A, and/or other stevia-based sweeteners.

11. An edible composition according to claim 2 containing a soy-protein.

12. An edible composition according to claim 2 containing KCl.

13. A stock solution formulated to be added to a foodstuff composition or a beverage composition, the stock solution comprising a compound selected from the group consisting of: N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro, N-linolenoyl-Pro; N-geranoyl-Met, N-palmitoyl-Met, N-palmitenoyl-Met, N-stearoyl-Met, N-oleoyl-Met, N-linoleoyl-Met, N-linolenoyl-Met, and edible salts thereof selected from chlorides, sulphates, phosphates, gluconates, sodium, citrates, carbonates, acetates and lactates.

14. A stock solution according to claim 13, wherein the stock solution is formulated to be added to an edible composition to provide the compound in an ultimate concentration of 1 ppb -10 ppm of the compound in the edible composition.

15. A stock solution according to claim 13, wherein the stock solution is effective in masking or modulating an undesired taste or off-taste caused by a natural sweetener selected from: sucrose, high fructose corn syrup, fructose and glucose, or a high intensity, non-nutritive sweetener selected from: aspartame, acesulfame K, sucralose, cyclamate, sodium saccharin, neotame, rebaudioside A, and/or other stevia-based sweeteners, contained in an edible composition, when the compound is present in the edible composition at a concentration of 1 ppb -10 ppm of the edible composition.

16. A stock solution according to claim 13, wherein the stock solution is effective in masking or modulating an undesired taste or off-taste caused by a soy-based product, contained in an edible composition, when the compound is present in the edible composition at a concentration of 1 ppb -10 ppm of the edible composition.

17. A stock solution according to claim 13, wherein the stock solution is effective in masking or modulating an undesired taste or off-taste caused by KCl, contained in an edible composition, when the compound is present in the edible composition at a concentration of 1 ppb -10 ppm of the edible composition.

Description

SYNTHESIS EXAMPLES

(1) 1.1 Route A: (DCC Method)

(2) In a 250 mL round-bottomed flask was mixed fatty acid (3.93 mmol) with 1-hydroxypyrrolidine-2,5-dione (0.498 g, 4.32 mmol) in dioxane (50 ml) to give a colorless solution. The solution was cooled to 10° C. and DCC (0.892 g, 4.32 mmol) was added while stirring. Stirring was continued for three hours at room temperature. The formed solids were filtered (dicyclohexylurea) and the filtrate was added to a solution of amino acid (6.48 mmol) in a 2% solution of sodiumbicarbonate (0.363 g, 4.32 mmol) in water. The reaction mixture was stirred for 4 hours at 50° C. Dioxane was evaporated and the aqueous residue was further diluted with water, acidified with a diluted hydrochloric acid solution and extracted with ethylacetate. Organic layers were combined, washed with brine, dried and evaporated to yield 1.3 g of a white solid. Product was purified by flash column chromatography, eluent DCM/methanol.

(3) 1 g of 85-90% pure product could be obtained.

(4) 1.2 Route B (DCC Method with Protection Group)

(5) Step 1:

(6) To a solution of an O-methylated amino acid (16.51 mmol) in DCM (100 ml) was added triethylamine (1.519 g, 15.01 mmol) at minus 15° C. A fatty acid (0.01 mmol) was added while stirring. A solution of DCC (15.01 mmol) in 10 mL of DCM was added dropwise at 0° C. The reaction mixture was stirred at 0° C. for 1 hour and stirring was continued at room temperature for 3 hours. The dicyclohexylurea was removed by filtration from the reaction mixture. Filtrate was washed with a saturated sodiumbicarbonate solution, diluted hydrochloric acid solution and water. Organic layer was separated, dried and evaporated to yield 3 g of an oil. This oil was purified by flash column chromatography, eluent DCM/methanol The intermediate ester compound could be isolated in a purity of 95%.

(7) Step 2:

(8) The O-methylated N-acyl-amino-acid (4.91 mmol) was dissolved in a mixture of Ethanol (8.00 ml) and water (8 ml). To this mixture was added a 32% solution of sodiumhydroxide (2.453 g, 19.63 mmol) and mixture was stirred at room temperature for three hours. Mixture stand over for 14 hours.

(9) After 14 hours the mixture was acidified with a concentrated hydrochloric acid solution (1.612 ml, 19.63 mmol), diluted with water and extracted with mtbe. Organic layer was separated, dried and evaporated. 1.3 g of a half solid yellow residue was obtained. NMR confirmed the structure of the title compound, purity 95%

(10) 1.3 Route C (Acid Chloride)

(11) An amino acid (20 mmol) was dissolved in a solution of sodiumhydroxide (54.5 mmol) in water (40 ml).

(12) Tetrahydrofuran (60 ml) was added. Fatty acid chloride (18.18 mmol) was added dropwise at room temperature. Stirring was continued for 2 hours. Mixture was diluted with water, acidified with a 37% solution of hydrochloric acid (2.99 ml, 36.4 mmol) and extracted with ethylacetate.

(13) Organic layers were combined, dried and evaporated.

(14) The residue contains about 20% free fatty acid according NMR. The solids were stirred with heptane for 30 minutes, filtered and dried. This resulted in 2.4 g of the title compound as a creamy colored solid. (purity 95%).

(15) 1.4 all Synthesized Compounds

(16) TABLE-US-00001 TABLE 1 List of synthesized compounds Carb- Struc- Amino oxylic ture acid acid Structure Route 1 ACC C10:0 0 C 2 ACC C10:2 A 3 ACC C16:0 C 4 ACC C18:0 C 5 ACC C18:1 C 6 ACC C18:2 A 7 GABA C10:0 C 8 GABA C12:0 C 9 GABA C12:1 C 10 GABA C10:2 C 11 GABA C14:0 0 C 12 GABA C16:0 C 13 GABA C16:1 A 14 GABA C18:0 C 15 GABA C18:1.sub.c C 16 GABA C18:1.sub.t C 17 GABA C18:2 A 18 GABA C18:3 A 19 GABA C22:1 C 20 Beta- alanine C16:1 A 21 Beta- alanine C18:1 0 C 22 Beta- alanine C18:2 A 23 Aspartic acid C10:0 C 24 Aspartic acid C10:2 B 25 Aspartic acid C16:0 C 26 Aspartic acid C18:0 C 27 Aspartic acid C18:1 C 28 Aspartic acid C18:2 A 29 Glutamic acid C10:0 C 830 Glutamic acid C16:0 C 31 Glutamic acid C16:1 0 A 32 Glutamic acid C18:0 C 33 Glutamic acid C18:1 C 34 Glutamic acid C18:2 A 35 Glutamine C10:0 C 36 Glutamine C12:0 C 37 Glutamine C10:2 A 38 Gutamine C16:0 C 39 Glutamine C18:0 C 40 Glutamine C18:1 C 41 Glutamine C18:2 0 A 42 Methionine C10:0 A 43 Methionine C12:0 A 44 Methionine C12:1 A 45 Methionine C16:0 A 46 Methionine C18:1 A 47 Methionine C18:2 A 48 Proline C10:2 A 49 Proline C16:0 C 50 Proline C16:0 C 51 Proline C18:2 0 A 52 Serine C10:2 B 53 Serine C16:0 C 54 Serine C18:1 C 55 Serine C18:2 A 56 Leucine C-8:0 C 57 Leucine C10:2 B 58 Leucine C16:0 C 59 Leucine C16:1 A 60 Leucine C18:0 C 61 Leucine C18:1 0 C 62 Leucine C18:2 B 63 Leucine C22:1 A 64 Isoleucine C18:1 C 65 Valine C16:0 C 66 Valine C18:0 C 67 Valine C18:1 C 68 Valine C18:2 A

2 NMR Data (Examples)

(17) ##STR00078##
2.1 Structure 5 ACC-C18:1

(18) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.88 (0=7.05 Hz, 3H, H—C(18)) 1.09-1.21 (m, 2H H—C(22,23)) 1.21-1.1.39 (m, 20H, H—C(4, 5, 6, 7, 12, 13, 14, 15, 16, 17)) 1.54-1.68 (m, 4H, H—C(3, 22, 23)) 1.91-2.07 (m, 4H, H—C(8, 11)) 2.18 (0=7.73 Hz, 2H, H—C(2)) 5.26-5.44 (m, 2H, H—C(9, 10)) 6.28 (s, 1H, H—N(19))

(19) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.13 (C(18) 18.01 (C(22, 23)) 22.69 (C(17)), 25.45 (C(3)), 27.19 (C(11) 27.23 (C11)) 29.16 (C4)) 29.18 (C6)) 29.26 (C(5)) 29.33 (C(13, 15)) 29.45 (C(14)) 29.72 (C(7)) 29.78 (C(12)) 31.91 (C(16, 21)) 33.47 (C(2)) 129.76 (C(10)) 129.99 (C(9)) 175.15 (C(1)) 177.39 (C(20))

(20) 2.2 Structure 7 GABA-C10:0

(21) ##STR00079##

(22) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.83-0.87 (m, 3H, H—C(10)) 1.18-1.29 (m, 12H, H—C(4, 5, 6, 7, 8, 9) 1.46 (quin, J=7.22 Hz, 2H, H—C(14)) 1.59 (quin, J=7.22 Hz, 2H, H—C(3)) 2.02 (t, J=7.39 Hz, 2H, H—C(2)) 2.19 (t, J=7.39 Hz, 2H, H—C(13)) 3.00-3.05 (m, 2H, H—C(15)) 7.77 (t, J=5.50 Hz, 1H, H—N(15)

(23) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.95 (C(10)) 22.09 (C(9)) 24.64 (C(14)) 25.29 (C(3)) 28.64 (C(5)) 28.66 (C(7)) 28.78 (C(6)) 28.90 (C(4)) 31.07 (C(13)) 31.27 (C(8)) 35.38 (C(2)) 35.77 (C(15)) 172.03 (C(1)) 174.21 (C(12))

(24) 2.3 Structure 8 GABA-C12:0

(25) ##STR00080##

(26) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.85 (0=6.87 Hz, 3H, H—C(12)) 1.15-1.33 (m, 16H, H—C(4, 5, 6, 7, 8, 9, 10, 11) 1.41-1.51 (m, 2H, H—C(3)) 1.59 (quin, J=7.22 Hz, 2H, H—C(16)) 2.02 (0=7.56 Hz, 2H, H—C(2)) 2.19 (0=7.56 Hz, 2H, H—C(15)) 3.02 (q, 1=6.53 Hz, 2H, (H—C(17)) 7.77 (0=5.33 Hz, 1H, H—N(13))

(27) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.95 (C(12)) 22.09 (C(11)) 24.64 (C(16((25.29 (C(3)) 28.64 (C(9)) 28.71 (C(15)) 28.77 (C(6)) 28.95 (C(8)) 29.00 (C(5)) 29.02 (C(4)) 31.06 (C(7)) 31.29 (C(10)) 35.77 (C(17)) 172.02 (C(1)) 174.20 (C14))

(28) 2.4 Structure 17 GABA-C18:2

(29) ##STR00081##

(30) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.89 (t, J=6.87 Hz, 3H, H—C(18)) 1.26-1.39 (m, 14H, H—C(4, 5, 6, 7, 15, 16, 17) 1.57-1.65 (m, 2H, H—C(3)) 1.84 (quin, J=6.96 Hz, 2H, H—C(22)) 2.05 (q, J=7.22 Hz, 4H, H—C(8), H—C(14)) 2.19 (0=7.73 Hz, 2H, H—C(2)) 2.40 (0=7.05 Hz, 2H, H—C(21)) 2.77 (0=6.87 Hz, 2H, H—C(11)) 3.33 (q, J=6.53 Hz, 2H, H—C(23)) 5.30-5.41 (m, 4H, H—C(9, 10, 12,13) 5.96 (br. s., 1H, H—N(19))

(31) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.08 (C(18) 22.58 C(17)) 24.74 (C3)) 25.63 (C(22)) 25.75 (C(11)) 27.20 (C8, 14)) 29.15 (C(6)) 29.26 (C(5, 21)) 29.35 (C(15)) 29.62 (C(4)) 31.49 C(7)) 31.52 C(16)) 36.73 C(2)) 38.84 (C23)) 127.90 (C12)) 128.06 (C(10)) 130.03 (C(9) 130.25 (C(13)), 174.17 (C(1) 177.43 (C(20))

(32) 2.5 Structure 22 Beta-Alanine-C18:2

(33) ##STR00082##

(34) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.85 (t, J=7.05 Hz, 3H, H—C(18)) 1.11-1.37 (m, 14H, H—C(4, 5, 6, 7, 15. 16, 17) 1.37-1.53 (m, 2H, H—C(3)) 1.94-2.08 (m, 6H, H—C(2, 8, 14) 2.34 (t, J=6.87 Hz, 2H, H—C(21)) 2.73 (t, J=6.70 Hz, 2H, H—C(11)) 3.13-3.27 (m, 2H, H—C(22)) 5.24-5.40 (m, 4H, H—C(12, 13)) 7.84 (t, J=5.67 Hz, 1H, H—N(19))

(35) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.91 (C(18)) 21.97 (C(17)) 25.21 (C(3)) 25.24 (C(11)) 26.60 (C(8)) 26.63 (C(14)) 28.58 (C(6)) 28.63 (C(5)) 28.68 (C(15)) 28.73 (C(4)) 29.04 (C(7)) 30.89 (C(16)) 33.98 (C(21)) 34.70 (C(22)) 35.27 (C(2)) 127.73 (C(10, 12)) 129.71 (C(9, 13)) (C(1)) 172.91 (C(20))

(36) ##STR00083##
2.6 Structure 28 Asp-C18:2

(37) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.86 (t, J=6.87 Hz, 3H, H—C(18)) 1.17-1.38 (m, 14H, H—C(4, 5, 6, 7, 15, 16, 17) 1.42-1.50 (m, 2H, H—C(3) 2.01 (q, J=7.10 Hz, 4H, H—C(8, 14) 2.06-2.10 (m, 2H, H—C(2)) 2.48-2.55 (m, 1H, H—C(22)) 2.62-2.68 (m, 1H, H—C(22)) 2.73 (t, J=6.87 Hz, 2H, H—C(11)) 4.49 (d, J=6.53 Hz, 1H, H—C(21)) 5.18-5.42 (m, 4H, H—C(9, 10, 12, 13) 8.09 (d, J=7.90 Hz, 1H, H—N(19))

(38) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.93 (C(18) 21.97 (C(17)) 25.21 (C(3), 26.60 (C(11)) 26.65 (C(8)) 28.55 (C(14)) 28.59 (C(6)) 28.70 (C(4)) 28.73 (C(5)) 29.05 (C(15)) 30.69 (C(7)) 30.89 (C(16)) 35.06 (C(2)) 36.25 (C(22) 48.49 (C(21)) 127.75 (C(10, 12)) 129.74 (C(9, 13) 171.73 (C(20)) 172.02 (C(1)) 172.61 (C23))

(39) 2.7 Structure 33 Glu-C18:1

(40) ##STR00084##

(41) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.88 (t, J=7.05 Hz, 3H, H—C(18) 1.19-1.39 (m, 20H, H—C(4, 5, 6, 7, 12, 13, 14, 15, 16, 17) 1.56-1.68 (m, 2H, H—C(3)) 1.94-2.04 (m, 4H—C(8, 12)) 2.08 (dt, J=13.83, 6.66 Hz, 1H, H—C(22)) 2.20-2.25 (m, 3H, H—C(22)) 2.43-2.55 (m, 2H, H—C(23)) 4.64 (q, J=6.87 Hz, 1H, H—C(21)) 5.30-5.38 (m, 2H, H—C(9,10)) 6.70 (d, J=7.22 Hz, 1H, H—N(19))

(42) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.13 (C(18) 22.69 (C(17)) 25.57 (C(3) 26.81 (C(22) 27.20 (C(11) 27.24 (C(8) 29.18 (C(6)) 29.22 (C(4)) 29.26 (C(5) 29.33 (C(13, 15) 29.55 (C(14)) 29.75 (C(7)) 29.78 (C(12)) 29.88 (C(23) 31.91 (C(16)) 36.36 (C(2)) 51.60 (C(21)) 129.71 (C(10)) 130.02 (C(9)) 174.62 (C(1)) 175.66 (C(20) 177.95 (C(24))

(43) 2.8 Structure 37 Gln-C10:2

(44) ##STR00085##

(45) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 1.56-1.61 (s, 3H, H—C(10) 1.67 (s, 3H, H—C(8)) 2.05-2.14 (m, 6H, H—C(4, 14, 15) 2.15-2.20 (m, 3H, H—C(9)) 2.39 (dd, J=15.46, 7.22 Hz, 2H, H—C(5)) 4.51 (d, J=6.19 Hz, 1H, H—C(13)) 5.01-5.13 (m, 1H, H—C(6) 5.60-5.72 (s, 1H, H—C(2)) 6.63 (br. s., 1H, H—N(11)) 7.14 (br. s., 2H, H.sub.2—N))

(46) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 17.69 (C(10) 18.52 (C(9) 25.67 (C(8)) 26.17 (C(5)) 30.95 (C(14)) 31.68 (C(15) 40.97 (C(4)) 51.92 (C(13)) 117.22 (C(2)) 123.14 (C(6)) 132.39 (C(7)) 156.33 (C(3)) 167.95 (C(1) 174.69 (C(16)) 177.12 (C(12))

(47) 2.9 Structure 44 Met-C12:1

(48) ##STR00086##

(49) .sup.1H NMR (300 MHz, CD.sub.3OD) ppm 0.92 (t, J=6.9 Hz, 3H, H—C(12)), 1.32-1.38 (m, 8H, H—C(8, 9, 10, 11), 1.63-1.73 (q, J=7.5 Hz, 2H, H—C(3)), 1.98-2.16 (m, 9H, H—C(4, 7, 16, 18), 2.28 (t, J=7.2 Hz, 2H, H—C(2)), 2.48-2.65 (m, 2H, H—C(17)), 4.56 (d, d, J=5.1, 9.9 Hz, 1H, 5H—C(15)), 5.33-5.46 (m, 2H, H—C(5, 6)).

(50) .sup.13C NMR (300 MHz, CD.sub.3OD) ppm 14.43 (C(12) 15.21 (C(18)) 23.71 (C(11)) 27.01 (C(4)) 27.70 (C(3)) 28.22 (C(7)) 30.08 (C(9)) 30.83 (C(17)) 31.31 (C(8)) 32.19 (C(16)) 32.95 (C(10)) 36.37 (C(2)) 52.59 (C(15)) 129.81 (C(5)) 131.80 (C(6)) 175.17 (C(14)) 176.28 (C(1))

(51) 2.10 Structure 46 Met-C18:1

(52) ##STR00087##

(53) .sup.1H NMR (300 MHz, CD.sub.3OD) ppm 0.90 (t, J=6.6 Hz, 3H, H—C(18)), 1.27-1.34 (m, 20H, H—C(4, 5, 6, 7, 12, 13, 14, 15, 16, 17), 1.60-1.65 (m, 2H, H—C(3)), 1.90-2.19 (m, 9H, H—C(8, 11, 22, 24), 2.25 et, J=6.3 Hz, 2H, H—C(C—H(2)), 2.49-2.62 (m, 2H, H—C(23)), 4.55 (d, d, J=4.8, 9.9 Hz, 1H, H—C(21)), 5.30-5.40 (m, 2H, H—C(9, 10).

(54) .sup.13C NMR (300 MHz, CD.sub.3OD) ppm 14.44 (C(18)), 15.24 (C(24)), 23.76, (C(17)) 26.96 (C(3)), 28.16 (C(11)), 30.26 (C(8)), 30.28 (C(6)), 30.37 (C(4)), 30.47 (C(5)), 30.62 (C(15), 30.85 ((C13, 14)), 30.87 (C(23)), 31.33 (C(7, 12)), 32.18 (C(22)), 33.12 (C(16)), 36.84 (C(2)), 52.60 (C(21)), 131.22 (C(9, 10)), 175.20 (C(1)), 176.61 (C(20)).

(55) 2.11 Structure 51 Proline-C18:2

(56) ##STR00088##

(57) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.78-0.85 (m, 3H, H—C(18)) 1.18-1.33 (m, 14H, H—C(4, 5, 6, 7, 15, 16, 17) 1.54-1.65 (m, 2H, H—C(3)) 1.84-1.92 (m, 1H, H_C(22)) 1.92-2.03 (m, 6H, H_C(8, 14, 23)) 2.26-2.32 (m, 2H, H—C(2)) 2.44 (ddd, J=12.29, 6.10, 2.92 Hz, 1H, H—C(22)) 2.70 (t, J=6.70 Hz, 2H, H—C(11)) 3.39 (td, J=9.62, 6.87 Hz, 1H, H—C(24)) 3.47-3.53 (m, 1H, H—C(24)) 4.53 (dd, J=8.08, 1.89 Hz, 1H, H—C(21)) 5.16-5.36 (m, 4H, H—C(9, 10, 12, 13)

(58) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.07 (C(18)) 22.57 (C(17)) 24.48 (C(3)) 24.79 C(23)) 25.62 (C11)) 27.05 (C(22)) 27.17 (C(8)) 27.19 (C(14)) 29.10 C(6)) 29.27 (C(4, 15)) 29.34 (C(5)) 29.60 C(7)) 31.51 C((16)) 34.45 C(2)) 47.98 C(24)) 60.25 (C(21)) 128.07 (C(12)) 128.07 (C(10)) 130.00 (C(9)) 130.24 C(13)) 171.87 (C(1)) 175.87 (C20))

(59) 2.12 Structure 55 Serine-18:2

(60) ##STR00089##

(61) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.85 (0=6.87 Hz, 3H, H—C(18) 1.18-1.35 (m, 16H, H—C(3, 4, 5, 6, 7, 15, 16, 17) 1.43-1.51 (m, 2H, H—C(2)) 2.01 (q, J=6.87 Hz, 4H, H—C(8, 14)) 2.12 (t, J=7.39 Hz, 2H, H—C(2) 2.73 (t, J=6.70 Hz, 2H, H—C(11)) 3.58 (dd, J=10.83, 4.30 Hz, 1H, H—C(22)) 3.65 (dd, J=10.83, 4.30 Hz, 1H, H—C(22) 4.21-4.27 (m, 1H, H—C(21)) 5.26-5.38 (m, 4H, H—C(9, 10, 12, 13)) 7.90 (d, J=7.90 Hz, 1H, H—N(19)

(62) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.91 (C(18)) 22.01 (C(17)) 25.22 (C(3)) 25.24 (C(11)) 26.63 (C(8)) 26.68 (C(14)) 28.65 (C(6)) 28.69 (C(4)) 28.77 (C(5. 15)) 20.09 (C(7)) 30.93 (C16)) 35.07 (C(2)) 54.55 (C(21)) 61.49 (C(22)) 127.74 (C(10, 12)) 129.72 (C(9, 13)) 172.19 (C(1)) 172.27 (C(20))

(63) 2.12 Structure 59 Leucine 16:1

(64) ##STR00090##

(65) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.85-0.90 (m, 3H, H—C(16)) 0.91-0.98 (m, 6H, H—C(22, 23)) 1.19-1.40 (m, 14H, H—C(4, 5, 6, 7, 12, 13, 14)) 1.49-1.75 (m, 7H, H—C(3, 15, 20, 21)) 2.01 (q, J=6.07 Hz, 4H, H—C(8, 11)) 2.24 (t, J=7.73 Hz, 2H, H—C(2)) 4.54-4.59 (m, 1H, H—C(19)) 5.24-5.43 (m, 2H, H—C(9, 10)) 6.14 (d, J=8.25 Hz, 1H, H—N(19))

(66) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.11 (C16)) 21.9 (C(15) 22.66 (C(22) 22.86 (C(23) 24.91 (C21)) 25.63 (C(3)) 27.18 (C(11)) 27.23 (C(8)) 28.99 (C(6)) 29.16 (C(4)) 29.20 (C(5)) 29.25 (C(13)) 29.71 (C(7)) 29.73 (C(12)) 31.79 (C(14)) 36.51 (C(2)) 41.32 (C(20)) 50.87 (C(19)) 129.73 (C(9)) 130.00 (C(10)) 173.95 (C(1)) 176.38 (C(18))

(67) ##STR00091##
2.13 Structure 61 Leu-C18:1

(68) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.77-0.84 (m, 3H, H—C(18)) 0.85-0.93 (m, 6H, H—C(24, 25)) 1.14-1.29 (m, 20H, H—C(4, 5, 6, 7, 12, 13, 14, 15, 16, 17) 1.48-1.59 (m, 3H, H—C(3, 22) 1.60-1.69 (m, 2H, C—H(22, 23) 1.90-1.99 (m, 4H, H—C(8, 11)) 2.17 (t, J=7.39 Hz, 2H, H—C(2)) 4.55 (td, J=8.51, 4.64 Hz, 1H, H—C(21)) 5.15-5.35 (m, 2H, H—C(9, 10) 5.95 (d, J=7.56 Hz, 1H, H—N(19))

(69) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 13.68 (C(18)) 21.43 (C(17)) 22.24 (C(25) 22.40 (C(24) 24.45 (C(23)) 25.14 (C(3)) 26.74 (C(11) 26.78 (C(8)) 28.71 (C(6)) 28.73 (C(4)) 28.78 (C(5)) 28.88 (C(13, 15)) 29.09 (C(14)) 29.26 (C(7)) 31.46 (C16)) 36.04 (C(2)) 40.70 (C(22)) 50.41 (C(21)) 129.28 (C(9, 10) 173.64 (C(1) 176.11 (C(20))

(70) ##STR00092##
Structure 65 Val-C16:0

(71) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.88 (0=7.05 Hz, 3H, H—C(16)) 0.95 (d, J=6.87 Hz, 3H, H—C(21)) 0.98 (d, J=6.87 Hz, 3H, H—C(20)) 1.19-1.37 (m, 24H, H—C(3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14) 1.59-1.71 (m, 2H, H—C(3)) 2.20-2.32 (m, 3H, H—C(3)) 4.59 (dd, J=8.59, 4.81 Hz, 1H, H—C(18)) 6.19 (d, J=8.59 Hz, 1H, H—N(17))

(72) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.13 C(16)) 17.70 C(20)) 19.02 C(21)) 22.71 C(15)) 25.78 C(3)) 29.25 C(6)) 29.35 C(9)) 29.38 (C(13) 29.52 C(5)) 29.64 C(4)) 29.68 (C(7, 10)) 29.72 C(8, 11, 12)) 31.00 (C(19)) 31.94 (C(14)) 36.69 (C(2)) 57.08 C(18)) 174.23 (C(1)) 175.49 C(22)

APPLICATION EXAMPLES

(73) Test on Tang (High Intensity Sweetener HIS Masking)

(74) In an orange flavoured Tang powdered soft drink (market product) sweetened with sucrose plus high intensity sweetener (aspartame and acesulfame-K) and containing citric acid, C18:2-gaba and C18:2-pro were tested.

(75) All samples were evaluated by expert tasters. Tasters were asked to describe the samples focusing on authentic taste, masking off notes of high intensity sweetener, mouthfeel & body, enhancement, richness, juiciness, long lastingness, salivation, sweetness

(76) Base is Orange Flavoured Tang

(77) Base: sweet, orange, licorice, and lingering high intensity sweetener off-notes, bitter, thin

(78) Base plus C18:2-gaba at 0.5 ppm: the off-notes of the high intensity sweetener were suppressed. Additionally, the sweet juicy orange notes and mouthfeel are enhanced

(79) Base plus C18:2-Pro at 1 ppm: the off-notes of the high intensity sweetener were suppressed. Additionally, the fresh, sweet juicy orange notes are enhanced, characteristic of authentic fresh orange fruit.

(80) Test on Soy Milk (Soy Protein Masking)

(81) In a soy milk (1.8% fat) sweetened with 5% sucrose by weight, flavoured with a proprietary milk flavour at a dosage of 0.1%, C18:2-gaba was added at 2 ppm

(82) Samples were evaluated by expert tasters. Tasters were asked to describe the samples focusing on authentic taste, masking of soy protein off notes, mouthfeel, fullness, salivation, sweetness, richness, long lastingness and fattiness.

(83) Soy milk, 5% sucrose, milk flavor @0.1%: sweet, dry, green, soy bean taste

(84) Soy milk, 5% sucrose, milk flavor @0.1%, C18:2-gaba at 2 ppm: good reduction of the undesirable soy bean off-taste, clean, rich, creamy and milky.

(85) Test on Liquid Margarine (KCL Masking)

(86) In Blueband liquid margarine (market product) with added KCL 0.8% and a proprietary masking flavour @0.01% 18:2 gaba was added at 2 ppm.

(87) Samples were evaluated by expert tasters. Tasters were asked to describe the samples focusing on authentic taste, masking of KCL off notes, mouthfeel, saltiness, fullness, salivation, long lastingness and fattiness.

(88) Base is Blueband, 0.8% KCL, proprietary masking @0.01%

(89) Base: metallic, buttery, bitter and soapy

(90) Base plus C18:2-gaba at 2 ppm. The composition was considered to exhibit a more saltiness, more mouthfeel, less metallic and bitter notes, more authentic butter.